Process for the polymerization of olefinic-containing monomers employing anionic initiators

ABSTRACT

Siloxy-terminated hydrocarbon polymers containing at least one polymer chain per molecule of the formula: ##STR1## wherein R 1 , R 2  and R 3  are independently selected from saturated and unsaturated aliphatic and aromatic radicals, A is a saturated hydrocarbon bridging group optionally containing at least one aromatic group and --(M)n -- represents a polymer of an olefinic monomer, n having a value such that the average molecular weight of the polymeric chain is from about 1000 to about 5,000,000, together with telechelic polymers and radial polymers containing this unit.

This application is a continuation-in-part of application Ser. No.08/238,738, filed May 5, 1994, now abandoned, which is a division ofSer. No. 07/920,368, filed as PCT/GB91/00187, Feb. 6, 1991, now U.S.Pat. No. 5,331,058.

This invention relates to a process for the polymerisation ofolefinic-containing monomers employing anionic initiators. The inventionalso relates to novel anionic initiators for use in said process, and topolymers produced by said process.

Highly useful polymeric products can be obtained by polymerisingolefinic-containing monomers in the presence of an organo-alkali metalinitiator and subsequently reacting the resulting polymer, containing anactive alkali metal end group or groups, with a reagent which willeither couple the polymer molecules or replace the alkali metal withmore stable reactive end groups.

It can be seen that such a polymerisation process will consistessentially of three stages:

a. Initiation, in which the monomeric material is contacted with amonofunctional or difunctional anionic initiator.

b. Propagation, in which the monomer is allowed to polymerise to formliving polymer chains with negatively charged ends, and

c. Termination, in which the living polymer chains are treated withsuitable reagents, generally to form monofunctionally or difunctionallyterminated polymers.

The presence of a reactive terminal group or groups on the ends of thepolymer molecules enables substantially more effective cures to takeplace. In the case of a polymer containing a reactive group on each ofits ends (a telechelic polymer) all of the polymer molecule will be tiedinto the cross-linked structure of the cured material.

The well defined structure produced by telechelic polymers in thenetworks of their cured products is the primary reason for theirincreased use as precursors in the commercial production of curedrobbery solids.

However, in order to meet the requirements of a modem synthetic rubberit is not enough that the polydiene produces effective cures nor thatthe cured product has a well defined cross linked structure, it is alsoimportant that the cured product possesses good elastomeric properties.In the case of polydienes the elastomeric quality of the cured productis dependent upon the 1,4-content of the polymeric diene. Generally, thehigher the 1,4-content of the polymer, the lower its glass transitiontemperature and the better the elastomeric properties of the curedproduct. It follows from this that any process chosen for the commercialproduction of polydienes (in particular telechelic polymers of1,3-dienes) must lead to a material having a high 1,4-content.

It is well known that monofunctional polyalkenes and high 1,4-contentmonofunctional polydienes can be prepared in inert non-polar hydrocarbonsolvents by initiating the reaction with a monofunctional anionicinitiator such as butyl lithium. The preparations of telechelicpolydienes, using corresponding difunctional initiators such as1,4-dilithiobutane, has hitherto required that the anionicpolymerisation reaction (propagation) takes place in the presence of asterically-hindered Lewis acid in order to ensure that the polymericproduct possesses a reasonable 1,4-content (typically 25-50%).Furthermore, the polymerisation reaction must take place in polarsolvents such as alkyl and cycloalkyl ethers because difunctionalinitiators are insoluble in non-polar solvents such as hydrocarbons, andthis has hitherto prevented the formation of polydienes with1,4-contents above about 50% which can be produced using theaforementioned monofunctional initiators in hydrocarbon solvents.

A further disadvantage associated with the use of difunctionalinitiators is that the choice of telechelic polymers which can beproduced at the termination of propagation is restricted to those havingidentical terminal groups at either end since the reagent used fortermination will react in a similar manner with both living ends of thegrowing polymer chain.

The main object of the present invention is to provide a new process forthe anionic polymerisation of an olefinic-containing monomer which canbe used to prepare telechelic polymers and yet avoids the disadvantagesassociated with the use of known difunctional initiators. It is afurther object of the present invention to provide a process for theanionic polymerisation of a conjugated 1,3-diene which produces apolymeric material having an enhanced 1,4-content. It is a yet furtherobject of the invention to provide a novel anionic initiator for use inthe present process.

Processes of the type described form the subject of U.S. Pat. No.5,331,058 granted to this applicant and the anionic initiator is thesubject of U.S. Pat. No. 5,362,699 granted to this applicant.

According to the first-mentioned patent, there is provided a process forthe anionic polymerisation of an olefinic-containing monomer comprisingcontacting the monomer in an inert solvent with a monofunctional silylether initiator of general formula I ##STR2## wherein R₁, R² and R³ areindependently selected from saturated and unsaturated aliphatic andaromatic radicals, A is a hydrocarbon bridging group containing from 1to 25 carbon atoms and B is an alkali metal.

The inert solvent is preferably a non-polar solvent such as ahydrocarbon, since anionic polymerisation in the presence of suchsolvents is known to produce, from 1,3-dienes, polydienes with high1,4-contents. Preferred solvents are aliphatic, alicyclic and aromatichydrocarbons, especially alkanes, cycloalkanes and cycloalkenes, havingfrom 3 to 12, preferably from 4 to 8, carbon atoms. Examples of suitablehydrocarbons are hexane, cyclohexane, toluene and benzene. Alkanes arethe most preferred solvents.

The olefinic monomer is preferably an alkene or an alkylene-substitutedaromatic or a 1,3-diene. The alkene, alkenyl-substituted aromatic or1,3-diene will be chosen from the group of unsaturated organic compoundsthat can be polymerised anionically (ie in a reaction initiated by anorgano alkali metal). Suitable alkene or alkenyl-substituted aromaticsinclude the optionally-substituted styrenes and vinylnaphthalenes.Suitable 1,3-dienes will preferably contain from 4 to 12, especiallyfrom 4 to 8, carbon atoms per molecule. Examples of these compoundsinclude the following: 1,3-butadiene; isoprene;2,3-dimethyl-1,3butadiene; 1,3-pentadiene;2-methyl-3-ethyl-1,3-butadiene; 3-methyl1,3-butadiene;2-methyl-3-ethyl-1,3-pentadiene; 1,3-hexadiene; 2-methyl-1,3-hexadiene;1,3-heptadiene; 3-methyl-3-heptadiene; 1,3-octadiene;3-butyl-1,3-octadiene; 3,4-dimethyl-1,3-hexadiene;3-n-propyl-1,3-pentadiene; 4,5-diethyl- 1,3-octadiene;phenyl-1,3butadiene; 2,4-diethyl-1,3-butadiene;2,3-di-n-propyl-1,3-butadiene; and 2-methyl-3-isopropyl-1,3-butadiene.

Among the dialkylbutadienes, it is preferred that the alkyl groupscontain from 1 to 3 carbon atoms. Of the above monomers 1,3-butadiene,isoprene, 2,3-dimethyl-1,3-butadiene and 1,3pentadiene are preferredwith 1,3-butadiene being particularly preferred. The dienes may bepolymerised alone, or in admixture with each other or with alkenes toform random copolymers, or by charging the dienes to the reactionmixture sequentially, either with each other or with alkenes, to formblock copolymers.

R¹, R² and R³ are preferably independently selected from alkyl, aryl,and alkaryl. More preferably, each of the radicals R¹, R² and R³contains from 1 to 10 carbon atoms. In order to reduce the reactivity ofthe siloxy group on the initiator, the radicals R¹, R², and R³ arepreferably not all methyl and preferably together contain at least 4,most preferably at least 5, carbons atoms. In this way, a degree ofsteric hindrance is introduced into the silyl group which inhibitsreaction between that group and the living ends of the growing polymerchain, especially when at least one of R¹, R² and R³ contain at leastthree, more especially at least four, carbon atoms. Polymer yield andpurity is also generally enhanced if at least one of R¹, R² and R³ isaryl, preferably phenyl or mono-substituted phenyl with themono-substituent group on the phenyl preferably being a C₁ -C₅ alkylgroup.

The spacer group A preferably contains at least two carbon atoms and ispreferably a saturated hydrocarbon group such as a branched or straightchain alkyl bridging group, though less preferably it may contain atleast one aromatic group such as a p-phenylene group. The principalcriteria for the selection of the group A is that it should besufficiently long to prevent the siloxy end group from interfering withthe polymerisation reaction, and it should provide the initiator withenhanced solubility in the inert, preferably non-polar solvent employedin the process. At the same time it should not add significantly to thesize and bulk of the terminal group at the end of the polymer chainbecause this will adversely affect the polymer's physical properties,especially its elastomeric properties. For these reasons, A is mostpreferably a straight chain alkyl bridging group of formula --(CH2)_(m)-- where m is an integer from 3 to 15, especially 3 to 10.

B is preferably lithium or sodium, and is most preferably lithium.

The present polymerisation reaction is preferably carried out at atemperature of between -30° C. and +30° C., especially between -10° C.and +10° C. The maximum temperature that may be employed in a givensystem will depend primarily on the physical properties, especially theboiling points, of the monomers and solvent chosen.

The amount of initiator added to the reaction mixture will be determinedby the structure of the monomer to be polymerised and by the desiredmolecular weight of the polymer. Typically for the production of apolymer containing a polymeric chain, derived from the polymerisation ofan olefinic-containing monomer and having a polymer molecular weightbetween about 1,000 and 100,000, between 0.5 and 50 mmoles of initiatoris used for each mole of monomer. The polymeric chain preferably has amolecular weight in the range 1.000 to 10.000 in which case preferablybetween 5 and 50 mmoles of initiator is used for each mole of monomer.

After propagation has been allowed to reach equilibrium; the singleactive ends on the living polymer chains may be terminated, by theaddition of suitable reagents which either donate a proton to orfunctionalise the anionic carbons. Proton donors such as water oralcohol yield terminally non-functional polymers. Preferably, however,the polymer chains will be terminated by a functional group. Examples ofsuitable end groups are:

a. hydroxyl, prepared by adding aldehydes, ketones or alkylene oxides,especially ethylene oxide;

b. carboxyl, prepared by adding CO₂ to the anionic polymer;

c. mercapto, prepared by adding sulphur, cyclic disulphides or cyclicsulphides such as ethylene or propylene sulphides;

d. amino and aziridine, prepared by adding aminoaldehydes or

e. epoxide, prepared by adding glycidaldehyde or diepoxides; and

f. metal halides, especially magnesium halides, prepared by adding ametal halide such as magnesium bromide.

Alternatively, the living polymer chains may be terminated by a di-orpolyfunctional coupling agent which is capable of terminating two ormore polymer chains through a single coupling agent molecule, therebylinking those chains together, with the advantage that a considerableincrease in polymer molecular weight can be achieved with littledegradation in polydispersivity. An example of such a coupling agent isSICl₄ which by displacement of its chloro substituent groups yields a"star" polymer with four organosiloxy-terminated polymer chainsradiation from a central silicon atom. Other polymers containing from 2or 3 to 20 polymer chain arms radiating from a central coupling agentmay be prepared utilising complex coupling agents such asmulti-functional organohalides typically containing from 2 or 3 to 20,preferably 2 to 4, halide groups, and other multi-functionalpolyhalosilanes preferably containing from 2 to 4 halide groups.Examples of such coupling agents are 1,2 ethylene dibromide, 1,4dichlorobutane, and dimethyldichlorosilane.

The organosiloxy protective groups remain unaffected by these varioustermination reactions. However, once propagation has been terminated,the relatively inert organosiloxy end groups on the polymer chains maythen be functionalised by reaction with a desilylation reagent to yield,after subsequent reaction with acid solution, reactive hydroxyl endgroups which are reactive in the sense that they can be reacted furtherto give rise to chemical cross-linking of the polymer chains. Preferredreagents for such desilylation reactions are the tetralkylammoniumfluorides, especially tetra-n-butylammonium fluoride, in polar solventssuch as alkyl or cycloalkyl ethers, especially tetrahydrofuran. Theseand other suitable desilylation reagents are discussed in Synthesis, 9,817-845 (1985), especially on page 828. Since aziridine and epoxidegroups may react with some of these reagents and/or acid solutions,these groups represent less preferred terminal groups on the other endsof the polymer chains prior to desilylation.

The present polymerisation process offers a number of significantadvantages over other known anionic polymerisation processes. First, themolecular weight distribution (M_(w) /M_(n)) is narrower than thatachieved by the analogous reaction using difunctional anionicinitiators. In the present case the molecular weight distribution (alsoknown as "polydispersivity") is typically about 1.1 whilst in thecompeting process M_(w) /M_(n) is for a polydiene generally 1.5 or abovein the absence of sterically-hindered Lewis acid and about 1.3 in thepresence of a sterically-hindered Lewis acid. The advantage offered by apolymer with a narrow M_(w) /M_(n) is that it produces a cured productwith a well defined network and, as a consequence, high strength.

The second advantage offered by the present process is the enhancementof the 1,4-content of the polydiene products it is capable of producingfrom the anionic polymerisation of 1,3 -dienes. In the present process,polydienes with a 1,4-content of 90% can be routinely prepared, whereaswith difunctional initiators, the maximum 1,4-content achievable isabout 50%. This advantage stems principally from the advantageoussolubility of the present initiator compounds in inert, non-polarhydrocarbon solvents which obviates the need to conduct polymerisationwithin a polar solvent.

A third advantage of the present invention is that it allows for thepreparation of polymers with a far greater diversity of functionalitythan has hitherto been achievable by anionic polymerisation.Monofunctional polymers result from termination with a proton donorfollowed by reactive functionalisation of the organosiloxy end groups(for example, to produce reactive hydroxyl end groups). Bifunctional(telechelic) polymers result from (a) functional termination of thepolymerisation reaction followed by (b) reactive functionalisation ofthe organosiloxy end groups. Indeed this can lead to telechelic polymershaving the same or different functional end groups depending on thereagents used in each of the steps (a) and (b), adding further to theaforesaid advantage of diversity. Di- and poly-functional polymersresult from termination of the polymerisation reaction with di- andpoly-functional coupling agents, followed by reactive functionalisationof the organosiloxy end groups.

The monofunctional silyl ether initiators which are used in the presentprocess are preferably prepared by the method of reacting, in an inertsolvent, the alkali metal B with an organosiloxyhalide of formula:II##STR3## where R¹, R² and R³ and A are as defined above and Z¹represents a halogen. The reaction may be represented by the equation:

    R.sup.1 R.sup.2 R.sup.3 Si--O--A--Z.sup.1 +2B→R.sup.1 R.sup.2 R.sup.3 Si--O--A--B+BZ.sup.1

Z¹ is preferably chlorine or bromine, and is most preferably chlorine.

The reaction, which is exothermic, is preferably performed in anon-polar solvents. Preferred solvents are aliphatic, alicyclic andaromatic hydrocarbons, especially alkanes, cycloalkanes andcycloalkenes, having from 3 to 12, preferably from 4 to 8, carbon atoms.Most preferably, the solvent is the same as that used in the subsequentpolymerisation reaction.

The alkali metal B, which is preferably lithium, is preferably providedin particulate form such as chopped fine wire (typically 1-2 mmdiameter) or freshly cut chips. The particles are preferably subjectedto high speed agitation in a fluid suspension prior to use to produce aclean metallic surface for further reaction. If lithium is used, then itpreferably contains from 0.5-3%, more preferably 1-2%, by weight ofsodium. In the absence of sodium, lithium tends to be unreactive towardsorganic halides. However, with increasing sodium content, there is anincreasing likelihood of undesirable side reactions and above 5 wt %sodium, the reagents may react violently. It has been found that inorder to ensure a high yield of product initiator, a stoichiometricexcess of alkali metal must be used, of preferably at least 21/2-fold,more preferably at least two-fold, most preferably at least 21/2-fold,with an upperlimit of preferably six-fold.

The reaction is preferably performed at a temperature of from 10° C. to50° C., more preferably from 20° C. to 40° C. At temperatures aboveabout 40° C., the production of undesirable organic by-products isobserved. The temperature can be controlled by cooling the reaction, andby ensuring that the major part of the organosiloxyhalide co-reagent isadded slowly to the alkali metal already in situ within the solvent. Areaction temperature of at least 30° C. is most preferred especially ifthe solvent is non-polar, to ensure that the reaction goes substantiallyto completion.

A further preferred condition of the reaction is that it should beperformed under a dry, oxygen-free, inert gas. The gas is preferably anoble gas such as helium or argon, since nitrogen will react with thealkali metal to form a metal nitride, especially if the metal islithium.

The advantage of this method of initiator preparation is that theprincipal by-products of the reaction (alkali metal halide and excessalkali metal) are insoluble inorganic solids rather than reactive,solvent-soluble organic compounds and so are easily separated from thesoluble initiator compound before it is used in the subsequentpolymerisation process.

The organosiloxyhalide compound of general formula II may be prepared byreacting, in an inert solvent an alcohol of general formula III:

    HO--A--Z.sup.1                                             III

with a silylhalide of general formula IV: ##STR4## wherein Z² is ahalogen which is the same or different to Z¹ and is preferably chlorine.

The terminated polymers resulting from the present process represent anovel group of polymers which may be used as intermediates in thepreparation of further, functionally terminated polymers, especiallytelechelic polymers, by the subsequent conversion of the protectiveorganosiloxy end groups into hydroxyl functional groups.

According to a third aspect of the present invention, therefore, thereis provided a siloxy-terminated hydrocarbon polymer containing at leastone polymer chain per molecule of general formula V: ##STR5## whereinR¹, R², and R³ are as defined above, A represents a saturatedhydrocarbon group optionally containing at least one aromatic group and--(M)_(n) -- represents a polymerised olefinic-containing monomer,preferably a polymerised alkene or, more preferably, a polymerised1,3-diene.

The polymer may be of general formula VI: ##STR6## wherein n has a valuesuch that the average molecular weight of the polymeric chain is fromabout 100.000 to about 5,000,000 and X is selected from carboxyl,hydroxyl, mercapto, amino and a metal halide, especially a magnesiumhalide, group. Such polymers are produced by terminating the livingpolymer chain produced by the present process by the monofunctionalreagents described above. Alternatively, the polymer may be of generalformula VII: ##STR7## wherein Y is the residue of a di- ormulti-functional halide coupling agent containing q functional halidegroups, where q is an integer from 2 to 20 (for example, 3), especiallyfrom 2 to 4, and r is an integer of at least 2 (for example, 3) which isless than or equal to q. For example, four-chain polymers of generalformula VII linked together by a single silicon atom can be produced byliving chain termination with the polyfunctional coupling agent SiCl₄ 'Similarly, polyfunctional organohalide coupling agents such as 1, 2ethylene dibromide and 1,4 dichlorobutane, and other polyfunctionalpolyhalosilane coupling agents such as dimethyldichlorosilane, may alsobe used.

The polymeric chain --(M)_(n) -- may have an average molecular weight inthe range of 1,000 to 10,000, especially 2.000 to 7,000 in which casethe polymers produced by the present invention will, if the polymermolecules contain a single polymeric chain --(M)_(n) --, normally beliquids. If desired however semi-solid and solid polymers with polymericchains --(M)_(n) -- having an average molecular weight of up to5,000,000 or above may also be prepared.

The present invention will now be described by way of Example only.

Materials

Butadiene (Matheson) was dried by passage through molecular sieves,calcium chloride and calcium hydride, before collecting in a graduatedvessel at -78° C.

Hexane (BDH) was dried over calcium hydride and fractionally distilledunder nitrogen, the fraction boiling at 67°-8° C. being collected.Lithium metal (Fluka) containing 1-2% sodium was supplied as a 30% w/wdispersion in mineral oil. The metal was washed repeatedly with hexanebefore charging with the reaction solvent so as to prepare a cleansilvery white metal surface.

Tert-butyldimethylsiloxy 1-chloro-hexyl ether was fractionallydistilled, under reduced pressure prior to use, the fraction boiling at184°-5° C. (100 mmHg) being collected.

Tert-butyldiphenylsiloxy 1-chloro-hexyl ether was distilled from akugelrohr (oven temperature 215° C.) under reduced pressure (1 mmHg),just prior to use.

Tetra-butyldiphenylsiloxy 1-chloro-propyl ether was distilled from akugelrohr (oven temperature 200° C.) under reduced pressure (1 mmHg),just prior to use.

Tetra-n-butylammonium fluoride (Aldrich) was supplied as a 1.0M solutionin tetrahydrofuran and used directly.

Tetrahydrofuran (BDH), stabilised with 0.1% quinol, was distilled undernitrogen when required after sufficient sodium benzophenone solution inTHF had been added to yield a permanent purple colour.

General Procedure

All experimental techniques were performed under an inert atmosphere, beit oxygen˜free nitrogen or argon. All glassware, except syringes, wascleaned by successive washing with 10% hydrofluoric acid, distilledwater and acetone. It was then dried and stored in an oven at 120° C.until required. All additions, excepting that of alkali metals, wereperformed via syringe.

EXAMPLE 1

A sixfold excess of lithium slurry (10 g) in mineral oil was placed intoa 500 ml 3-necked round bottom flask equipped with serum cap, argoninlet/outlet, water condenser, thermometer and magnetic follower. Theslurry was then repeatedly washed with hexane, by high speed agitation,until a clean silvery white metal surface was obtained. The lithiummetal was then charged with further hexane (100 ml) which was to act asthe reaction solvent. The temperature inside the reaction flask was thenraised to 35° C. and allowed to reach thermal equilibrium over the spaceof thirty minutes.

Freshly distilled tert-butyldimethyl (tBDM-) siloxy-1chlorohexyl ether(5 g, 0.02 mol) was injected into the reaction vessel. A primaryexotherm was observed to commence after 5-10 minutes. This exotherm wascontrolled by the utilisation of cold air cooling which maintained theflask temperature below 45° C. throughout the course of the reaction.Four further aliquots of tBDM-siloxy-1-chlorohexyl ether (4×5 g, 0.08mol) were added over a period of 1-2 hours. The reaction was allowed toproceed for a further 2 hours before allowing the products to settleinside the flask. The crude supernatant hexane solution oftBDM-siloxy-1lithiohexyl ether could then be extracted via syringe andutilised in various reactions, or simply quenched with methanol toproduce tBDM-siloxy hexane (Yield 95%). The yield of the reaction wasconfirmed by 'H n.m.r. spectroscopy and i.r. spectroscopy.

EXAMPLE 2

The procedure of Example 1 was repeated except that the species to belithiated was tert-butyldiphenyl (t-BDP-) siloxy-1-chlorohexyl etherrather than tert-butyldimethylsiloxy-1-chlorohexyl ether. The resultantyield of the reaction was again greater than 90%.

EXAMPLE 3

The procedure of Example 1 was repeated except that the reaction wasexecuted within the temperature range 20°-30° C., and the reactionsolvent was diethylether instead of n-hexane. The resultant yield of thereaction was again greater than 90%.

EXAMPLE 4

The procedure of Example 1 was repeated except that the species to belithiated was tert-butyldiphenylsiloxy-1-chloropropyl ether rather thantert-butyldimethylsiloxy-1-chlorohexyl ether. The reaction was executedwithin the temperature range 20°-30°C., and the reaction solvent wasdiethylether instead of n-hexane. The resultant yield of the reactionwas again greater than 90%.

EXAMPLE 5

The procedure of Example 1 was repeated except that the species to belithiated was tert-butyldiphenylsiloxy-1-chloropropyl ether rather thantert-butyldimethylsiloxy-1-chlorohexyl ether. The reaction was executedwithin the temperature range 20°-300° C. The resultant yield of thereaction was only 25% after 17 hours.

                  TABLE 1                                                         ______________________________________                                        The Effect of Temperature and Solvent Upon the Preparative Yield              of Trialkyl/aryl Siloxy Lithioalkyl Ethers                                    Trialkyl/Arylsiloxy                                                           Lithioalkyl ether                                                                            Solvent   Temperature                                                                             Yield                                      ______________________________________                                        tBDM-siloxy lithiohexyl ether                                                                Hexane    35-40° C.                                                                        >90%                                       "              Ether     20-30° C.                                                                        >90%                                       tBDP-siloxy lithiohexyl ether                                                                Hexane    35-40° C.                                                                        >90%                                       tBDP-siloxy lithiopropyl ether                                                               Ether     20-30° C.                                                                        >90%                                       "              Hexane    20-30° C.                                                                          25%                                      ______________________________________                                    

EXAMPLE 6

Hexane (250 ml) was placed in a 500 ml round bottom 3-necked flaskequipped with magnetic follower, thermometer, serum cap and nitrogeninlet/outlet. The reaction vessel was then chilled to -78° C. andbutadiene (30 ml) distilled into the system. The reaction mixture wasthen gradually allowed to warm to -5° C. and tBDM-siloxy 1-lithiohexylether (0.011 mol) in hexane solution from Example 1 was introduced byinjection in order to initiate polymerisation. Propagation was allowedto proceed at this temperature for an hour, before the ice bath wasremoved and the reaction mixture gradually allowed to reach roomtemperature. Propagation was then allowed to continue at roomtemperature for a further 16 hours. Termination of the living ends wasthen accomplished typically by the injection of a five-fold excess ofmethanol (1 ml) to yield a water white polymer solution. This wassubsequently reduced in volume by rotary evaporation, precipitated intoexcess methanol (1000 ml) and the crude polymer syrup collected ondecanting. The work up produced a monofunctional polybutadiene with asiloxyl group on one end of the polymer chain. The product was found tobe of low molecular weight (2,100), to be relatively monodisperse (M_(n)/M_(w) =1.1) and to possess a high 1,4 percentage content (89%).

The molecular weight of the product was determined by gel permeationchromatography (gpc) in which measurements were carried out using aWaters 840 chromatograph fitted with refractive index and ultra˜violetdetectors in series. Four styragel columns (Polymer Laboratories) ofporosity 10⁵ A, 10⁴ A, 10³ A and 10² A were used, and the molecularweight was determined from a universal polystyrene calibration curveusing the Mark-Houwinck coefficients a=0.693, K=4.03×10⁻⁴ (high 1,2) andK=4.57×10⁻⁴ (high 1,4).

The percentage 1,4 content of the product was determined by 'H nuclearmagnetic resonance (nmr) spectroscopy in which measurements were carriedout on a Varian Associates EM 60 MHz spectrometer, samples of thepolymer being prepared as 10% w/v solutions in deuterochloroform.

EXAMPLE 7

The procedure of Example 6 was repeated except the reaction wasinitiated with tBDP-siloxy lithiohexyl ether from Example 2 rather thanwith tBDM-siloxy lithiohexyl ether.

EXAMPLE 8

The procedure of Example 6 was repeated except that the reaction wasterminated with excess ethylene oxide rather than excess methanol. Theusual work up procedure produced a bifunctional polybutadiene, with ahydroxyl group at one end of the chain and a siloxyl group at the other.

EXAMPLE 9

The procedure of Example 6 was repeated except that the reaction wasterminated with exactly 0.0055 mol of dichlorodimethylsilane rather thanexcess methanol. The usual workup procedure produced a difunctionalpolybutadiene (M_(n) /M_(w) between 1.1 and 1.2 and % 1,4 contentbetween 87% and 91%) possessing siloxyl groups at both ends and acentral dimethylsilyl chain-linking group.

EXAMPLE 10

Siloxyl terminated polybutadiene (1 g) from Example 6 was dissolved intetrahydrofuran (20 ml) in a 100 ml round bottom 3-necked flask equippedwith magnetic follower, serum cap and nitrogen inlet/outlet.Tetra-n-butylammonium fluoride (1.0M) in tetrahydrofuran (1.1 ml) wasthen added by injection and the reaction allowed to proceed at 20° C.for 2 hours. Afterwards the solution was added dropwise to excessmethanol, allowed to settle and the liquors decanted off to yield a paleyellow syrup, which was identified as monofunctional hydroxyl terminatedpolybutadiene (M_(n) /M_(w) =1.15, and % 1,4 content=90%).

EXAMPLE 11

The procedure of Example 10 was repeated using as the starting polymerthe siloxy-terminated polybutadiene products of Example 7 rather thanthe product of Example 6, to yield a monofunctional hydroxy-terminatedpolybutadiene (M_(n) /M_(w) between 1.1 and 1.2, and % 1,4 contentbetween 87% and 91%).

EXAMPLES 12 and 13

The procedure of Example 10 was repeated using as the starting polymerthe siloxy-terminated polybutadiene products of Examples 8 and 9 in turnrather than the product of Example 6. In both cases, the siloxy groupson the starting polymers were replaced by hydroxy groups, to yielddifunctional hydroxy-terminated polybutadienes (M_(n) /M_(w) between 1.1and 1.2,% 1,4 content between 87% and 91%).

EXAMPLE 14

The procedure of Example 6 was repeated except that the amount ofbutadiene used was 30 ml (0.0041 mol) and the amount of tBDM-siloxy1-lithiohexyl ether was 0.00035 mol). The usual work up procedureproduced a bifunctional polybutadiene with a hydroxyl group at one endof the chain and a siloxyl group at the other end. The product was foundto be of very high molecular weight (3,500,000) and had a narrow M_(w)/M_(n) of 1.24. Because of the very high molecular weight it was notpossible to carry out nmr spectroscopy of the product though the1,4-content would be expected to be of the order of 90%.

EXAMPLE 15

The procedure of Example 6 was repeated except that the amount ofbutadiene used was 50 ml (0.0069 mol) and the amount of tBDM-siloxy1-lithiohexyl ether was 0.00018 mol). The usual work-up procedureproduced a bifunctional polybutadiene with a hydroxyl group at one endof the chain and a siloxyl group at the other. The product was found tobe of very high molecular weight (4,900,000) and had a narrow M_(w)/M_(n) of 1.27. As with the product of Example 14 the very highmolecular weight of the present product precluded its analysis by nmr.

We claim:
 1. A siloxy-terminated hydrocarbon polymer having the formulaVI: ##STR8## wherein R¹, R² and R³ are independently selected fromsaturated and unsaturated aliphatic and aromatic radicals, A is asaturated hydrocarbon bridging group optionally containing at least onearomatic group, --(M)_(n) -- represents a polymer of anolefinic-containing monomer n having a value such that the averagemolecular weight of the polymeric chain is from about 100,000 to5,000,000 and X is selected from carboxyl, hydroxyl, mercapto, amino anda metal halide group.
 2. A siloxy-terminated hydrocarbon polymeraccording to claim 1 wherein each of R¹, R² and R³ contain from 1 to 10carbon atoms and R¹, R² and R³ together contain at least 5 carbon atoms.3. A siloxy-terminated hydrocarbon polymer according to claim 1 whereinA is --(CH₂)_(m) -- where m is an integer from 3 to
 15. 4. Asiloxy-terminated hydrocarbon polymer according to claim 1 wherein themonomer is an alkene or an alkenyl-substituted aromatic or a 1,3-diene.5. A siloxy-terminated hydrocarbon polymer according to claim 4 whereinthe monomer is a 1,3-diene.
 6. A siloxy-terminated hydrocarbon polymeraccording to claim 1 wherein the polymer has a polydispersivity of about1.1 and a 1,4-content of the order of 90%.
 7. Siloxy-terminatedhydrocarbon polymer containing at least one polymer chain per moleculeof formula V ##STR9## wherein R¹, R² and R³ are independently selectedfrom saturated and unsaturated aliphatic and aromatic radicals, A is--(CH₂)_(m) --where m is an integer from 3 to 15 and --(M)_(n) --represents a polymer of an olefinic containing monomer, n having a valuesuch that the average molecular weight of the polymeric chain is fromabout 1000 to about 5,000,000.
 8. Siloxy-terminated hydrocarbon polymeraccording to claim 7 wherein each of R¹, R² and R³ contains from 1 to 10carbon atoms and R¹, R² and R³ together contain at least 5 carbon atoms.9. Siloxy-terminated hydrocarbon polymer according to claim 7 where themonomer is an alkene or an alkenyl-substituted aromatic or a 1,3-diene.10. Siloxy-terminated hydrocarbon polymer according to claim 9 whereinthe monomer is a 1,3-diene.
 11. Siloxy-terminated hydrocarbon polymeraccording to claim 7 having a polydispersivity of about 1.1. 12.Siloxy-terminated hydrocarbon polymer containing at least one polymerchain per molecule of formula V ##STR10## wherein R¹, R² and R³ areindependently selected from saturated and unsaturated aliphatic andaromatic radicals, A is a saturated hydrocarbon bridging groupoptionally containing at least one aromatic group and --(M)_(n) --represents a polymer of an olefinic containing monomer, n having a valuesuch that the average molecular weight of the polymeric chain is fromabout 1000 to about 5,000,000 and wherein said polymer has a 1,4-contentof about 90%.
 13. Siloxy-terminated hydrocarbon polymer according toclaim 12 wherein each of R¹, R² and R³ contains from 1 to 10 carbonatoms and R¹, R² and R³ together contain at least 5 carbon atoms. 14.Siloxy-terminated hydrocarbon polymer according to claim 12 wherein themonomer is an alkene or an alkenyl-substituted aromatic or a 1,3-diene.15. Siloxy-terminated hydrocarbon polymer according to claim 14 whereinthe monomer is a 1,3-diene.
 16. Siloxy-terminated hydrocarbon polymeraccording to claim 12 having a polydispersivity of about 1.1. 17.Siloxy-terminated hydrocarbon polymer containing at least one polymerper chain per molecule of formula VII ##STR11## where R¹, R² and R³ areindependently selected from saturated and unsaturated aliphatic andaromatic radicals, A is --(CH₂)_(m) -- where m is an integer from 3 to15, --(M)_(n) -- represents a polymer of an olefinic-containing monomer,n having a value such that the average molecular weight of the polymericchain is from about 1000 to 5,000,000 and Y is the residue of amulti-functional halide coupling agent containing q functional halidegroups where q is an integer from 3 to 20, and r is an integer of atleast 3 which is less than or equal to q.
 18. Siloxy-terminatedhydrocarbon polymer containing at least one polymer chain per moleculeof formula VII ##STR12## where R¹, R² and R³ are independently selectedfrom saturated and unsaturated aliphatic and aromatic radicals, A is asaturated hydrocarbon group optionally containing at least one aromaticgroup, --(M)_(n) -- represents a polymer of an olefinic-containingmonomer, n having a value such that the average molecular weight of thepolymeric chain is from about 1000 to 5,000,000, Y is the residue of themulti-functional halide coupling agent silicon tetrachloride and r is aninteger of at least
 3. 19. Siloxy-terminated hydrocarbon polymercontaining at least one polymer chain per molecule of formula VII##STR13## where R¹, R² and R³ are independently selected from saturatedand unsaturated aliphatic and aromatic radicals, A is a saturatedhydrocarbon group optionally containing at least one aromatic group,--(M)_(n) -- represents a polymer of au olefinic-containing monomer, nhaving a value such that the average molecular weight of the polymericchain is from about 1000 to 5,000,000 and Y is the residue of amulti-functional halide coupling agent containing q functional halidegroups where q is an integer from 3 to 20, and r is an integer of atleast 3 which is less than or equal to q, wherein said polymer has apolydispersivity of about 1.1 and a 1,4-content of about 90%.